title: Defining the electronic and geometric structure of one-electron oxidized copper-bis-phenoxide complexes.
abstract: The geometric and electronic structure of an oxidized Cu complex ([CuSal](+); Sal = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) with a non-innocent salen ligand has been investigated both in the solid state and in solution. Integration of information from UV-vis-NIR spectroscopy, magnetic susceptibility, electrochemistry, resonance Raman spectroscopy, X-ray crystallography, X-ray absorption spectroscopy, and density functional theory calculations provides critical insights into the nature of the localization/delocalization of the oxidation locus. In contrast to the analogous Ni derivative [NiSal](+) (Storr, T.; et al. Angew. Chem., Int. Ed. 2007, 46, 5198), which exists solely in the Ni(II) ligand-radical form, the locus of oxidation is metal-based for [CuSal](+), affording exclusively a Cu(III) species in the solid state (4-300 K). Variable-temperature solution studies suggest that [CuSal](+) exists in a reversible spin-equilibrium between a ligand-radical species [Cu(II)Sal(*)](+) (S = 1) and the high-valent metal form [Cu(III)Sal](+) (S = 0), indicative of nearly isoenergetic species. It is surprising that a bis-imine-bis-phenolate ligation stabilizes the Cu(III) oxidation state, and even more surprising that in solution a spin equilibrium occurs without a change in coordination number. The oxidized tetrahydrosalen analogue [CuSal(red)](+) (Sal(red) = N,N'-bis(3,5-di- tert-butylhydroxybenzyl)-1,2-cyclohexane-(1R,2R)-diamine) exists as a temperature-invariant Cu(II)-ligand-radical complex in solution, demonstrating that ostensibly simple variations of the ligand structure affect the locus of oxidation in Cu-bis-phenoxide complexes.
authors.affiliation: Department of Chemistry, Stanford University, Stanford, California 94305, USA.
authors.forename: Tim
authors.initials: T
authors.lastname: Storr
authors.forename: Pratik
authors.initials: P
authors.lastname: Verma
authors.forename: Russell C
authors.initials: RC
authors.lastname: Pratt
authors.forename: Erik C
authors.initials: EC
authors.lastname: Wasinger
authors.forename: Yuichi
authors.initials: Y
authors.lastname: Shimazaki
authors.forename: T Daniel P
authors.initials: TD
authors.lastname: Stack
mesh_terms: D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004583:Electrons; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010087:Oxides / Q000737:chemistry*; D012996:Solutions; D013053:Spectrophotometry; D013059:Spectrum Analysis, Raman; D013696:Temperature
chemical_list: D010087:Oxides; D012996:Solutions; D003300:Copper